WO2021109030A1 - Organic-inorganic nanocomposite antifouling coating layer for environmentally friendly antifouling coating and preparation method therefor - Google Patents

Abstract

Disclosed are an organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling coating and a preparation method therefor. The organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling coating comprises the following preparation raw materials: nanoparticles modified by a silane coupling agent, a (methyl)acrylate and silyl (methyl)acrylate, and a silyl (methyl)acrylate copolymer. The organic-inorganic nanocomposite antifouling coating layer for an environmentally friendly antifouling coating can self-refresh the surface thereof, has strong hydrophobicity, can efficiently reduce the accumulation of marine organisms and reduce dirt adhesion, is environmentally friendly, and in addition has an excellent antifouling effect and has wide application prospects.

Description

Organic-inorganic nano composite anti-fouling coating for environment-friendly anti-fouling coating and preparation method thereof Technical field

The invention relates to the technical field of antifouling coatings, in particular to an organic-inorganic nano composite antifouling coating for environment-friendly antifouling coatings and a preparation method thereof.

Background technique

The solid parts and ships in the seawater often suffer from marine biological fouling. Fouling accelerates metal corrosion, causing the ship to slow down and increase fuel consumption.

In order to prevent the adhesion and growth of marine organisms, the antifouling coatings currently used on a large scale in the market are still antifouling coatings containing antifouling agents, especially cuprous oxide.

EP1476509 discloses a self-polishing antifouling paint, which contains inorganic antifouling agents such as copper oxide and copper thiocyanate, as well as organic antifouling agents such as SeaNine211, and Irgarol1051. The release of antifouling agents is not friendly to the marine environment and is easy to Cause antifouling agents to accumulate in marine organisms.

The invention patent with publication number CN1101841C discloses a silicate-compliant antifouling coating, which is used to prevent marine organisms from adhering to the surface of ships, marine facilities, etc., and at the same time extend the antifouling period of the antifouling paint. However, the coating It is composed of silicate environmentally friendly antifouling agent with organic tin, cuprous oxide, copper sulfate and other components as a composite environmentally friendly antifouling agent, and adding film-forming resin, dispersant, anti-settling agent and appropriate amount of organic solvent. The antifouling paint of the invention uses cuprous oxide and organotin as an environmentally friendly antifouling agent, and the environmentally friendly antifouling agent can cause pollution and harm to the ocean.

In order to be more environmentally friendly, a biofouling release coating without antifouling agent has been developed. Patent Publication No. WO2013107827 discloses a fouling release antifouling coating, which has the advantage of being friendly to the marine environment and can maximize However, this coating is preferably applied to ships with a speed of 15 knots, and when the sailing is slow or stationary, the surface of the coating cannot be updated, the application effect is not ideal, and it is easy to be polluted by dirt.

The invention solves the above-mentioned anti-fouling problem, prepares an organic-inorganic nano composite coating, does not contain an anti-fouling agent, can self-renew the surface, is environmentally friendly, and has a certain antifouling effect.

Summary of the invention

In order to solve the problem that the existing antifouling paints containing antifouling agents are likely to cause marine pollution, as mentioned in the above background art, the present invention provides an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings. Including the following preparation materials: Nanoparticles (PG-NPs) modified by silane coupling agent (SCA), (meth)acrylate, silyl (meth)acrylate, and silyl (meth)acrylate copolymer .

It should be noted that in this solution, the (meth)acrylate includes methacrylate and acrylate; the silyl (meth)acrylate includes silyl methacrylate and silyl acrylate; The silyl (meth)acrylate copolymer includes a silyl methacrylate copolymer and a silyl acrylate copolymer.

On the basis of the above solution, it further includes the following parts by weight of raw materials: the silyl (meth)acrylate copolymer is 4-40 parts, the silane coupling agent (SCA), (methyl) Acrylate and silyl (meth)acrylate modified nanoparticles (PG-NPs) are 61 to 95 parts.

On the basis of the above solution, further, the nanoparticles (PG-NPs) modified with silane coupling agent (SCA), (meth)acrylate, and (meth)silyl acrylate (PG-NPs) include the following preparation raw materials : Nanoparticles (G-NPs) modified by silane coupling agent (SCA), (meth)acrylate, silyl (meth)acrylate, initiator and organic solvent B.

On the basis of the above solution, further, the nanoparticles (PG-NPs) modified with silane coupling agent (SCA), (meth)acrylate, and (meth)silyl acrylate (PG-NPs) comprise the following parts by weight The raw materials: the silane coupling agent (SCA) modified nanoparticles (G-NPs) is 10-30 parts, the (meth)acrylate is 1-20 parts, the (meth)acrylic acid The silyl ester is 20-40 parts, the initiator is 1-5 parts, and the organic solvent B is 10-50 parts.

On the basis of the above solution, further, the (meth)acrylate is any of methyl methacrylate methyl, ethyl acrylate, propyl methacrylate, butyl methacrylate, and isooctyl acrylate. One or more compositions;

On the basis of the above solution, further, the (meth)acrylate is 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate A combination of any one or more of the esters; the use of hydroxylated monomers helps to modify the hydrolysis rate of the nanoparticles, so that the particles are released quickly;

It should be noted that in this solution, the (meth)acrylate includes methacrylate and acrylate; the 2-hydroxyethyl (meth)acrylate includes 2-hydroxyethyl methacrylate and acrylic acid. 2-hydroxyethyl; the 2-hydroxypropyl (meth)acrylate includes 2-hydroxypropyl methacrylate and 2-hydroxypropyl acrylate; the 2-hydroxybutyl (meth)acrylate includes methyl 2-hydroxybutyl acrylate and 2-hydroxybutyl acrylate.

On the basis of the above solution, further, the structural formula of the silyl (meth)acrylate is as follows:

Wherein, R is H or CH ₃ , and R ₁ , R ₂ , and R ₃ are alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups having 1 to 20 carbon atoms.

On the basis of the above solution, further, the silyl (meth)acrylate is trimethylsilyl acrylate, triethylsilyl acrylate, triisopropylsilyl acrylate, tributyl silyl acrylate Ester, trimethylsilyl methacrylate, triethylsilyl methacrylate, triisopropylsilyl methacrylate, and tributylsilyl methacrylate Things.

On the basis of the above solution, further, the organic solvent B is any one or a combination of aromatic hydrocarbon solvents, ester solvents, ketone solvents or ether solvents.

On the basis of the above solution, further, the aromatic hydrocarbon solvent is any one or a combination of toluene and xylene.

On the basis of the above solution, further, the ester solvent is any one or a combination of two of butyl acetate and ethyl acetate.

On the basis of the above solution, further, the ketone solvent is any one or a combination of two of methyl ethyl ketone, methyl ethyl ketone, or cyclohexanone.

On the basis of the above solution, further, the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether.

On the basis of the above scheme, further, the initiator is benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile, azo Any one or a combination of diisovaleronitrile.

On the basis of the above solution, further, the silane coupling agent (SCA) modified nanoparticles (G-NPs) include the following preparation materials: nanoparticles, silane coupling agent (SCA), and organic solvent A.

On the basis of the above solution, further, the silane coupling agent (SCA) modified nanoparticles (G-NPs) include the following parts by weight of raw materials: the nanoparticles are 5-25 parts, the silane The coupling agent (SCA) is 10 to 51 parts, and the organic solvent A is 15 to 45 parts.

On the basis of the above solution, further, the organic solvent A is any one or a combination of hydrocarbon solvents and alcohol solvents.

On the basis of the above solution, further, the hydrocarbon solvent is any one or a combination of two of toluene, xylene, and trimethylbenzene.

On the basis of the above solution, further, the alcohol solvent is any one or a combination of two of n-butanol, isobutanol, and phenethyl alcohol.

On the basis of the above solution, further, the nano particles are one of nano silica, nano titanium dioxide, nano zinc oxide or nano aluminum oxide.

On the basis of the above solution, further, the particle size of the nanoparticles is 10-40 nm.

On the basis of the above solution, further, the silane coupling agent (SCA) is one of KBE-1003, KBM503, and KBM5103.

On the basis of the above solution, further, the solid content of the silyl (meth)acrylate copolymer is 55%.

On the basis of the above solution, further, the viscosity of the silyl (meth)acrylate copolymer is 10-15 poise.

On the basis of the above solution, further, the weight average molecular weight of the silyl (meth)acrylate copolymer is 10,000 to 15,000.

The invention provides a preparation method of an organic-inorganic nano composite anti-fouling coating for environment-friendly anti-fouling coatings, which comprises the following steps:

Add the silyl (meth)acrylate copolymer solution to the preparation container, and add nanoparticles modified with silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate while dispersing (PG-NPs), the rotation speed of the dispersion is preferably 500 rpm, and then the high-speed dispersion is preferably carried out, the rotation speed of the high-speed dispersion shown is preferably 2000-2500 rpm, and the duration of the high-speed dispersion is preferably 15 min, which can be obtained;

Wherein, the preparation container is preferably a dispersion tank; the silyl (meth)acrylate copolymer solution is preferably a silyl (meth)acrylate copolymer SP-Si solution prepared by the method disclosed in patent US7691938B2, and The solid content is 55%, the viscosity is 10-15 poise, and the weight-average molecular weight is 10,000-15,000.

On the basis of the above scheme, further, the nanoparticles (PG-NPs) modified by silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate include the following preparation steps :

Add organic solvent B and silane coupling agent (SCA) modified nanoparticles (G-NPs) into the preparation container, and heat to 80-115°C under a protective gas atmosphere. The protective gas is preferably nitrogen. Then, within 5-10 hours, drop the mixture of (meth)acrylate, silyl (meth)acrylate, and initiator into the preparation container and keep it heated. After the addition is complete, centrifuge and wash. The washing is preferably repeated three times of centrifugal washing to obtain nanoparticles (PG-NPs) modified with silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate;

Wherein, the preparation container is preferably a four-necked flask.

On the basis of the above solution, further, the silane coupling agent (SCA) modified nanoparticles (G-NPs) include the following preparation steps:

Put the organic solvent A and the nanoparticles into the preparation container, and ultrasonically disperse. The ultrasonic dispersion time is preferably 20min. Under a protective gas atmosphere, heat to 40-60°C. The protective gas is preferably nitrogen. Within 3-6 hours, drop the silane coupling agent (SCA) into the preparation container and keep it heated. After the addition is complete, centrifuge and wash. The centrifugal wash is preferably repeated three times to obtain the silane coupling agent. Agent (SCA) modified nanoparticles (G-NPs);

Wherein, the preparation container is preferably a four-necked flask.

On the basis of the above solution, further, the nanoparticles modified by the silane coupling agent include the following parts by weight of raw materials: the nanoparticles are 5-25 parts, and the silane coupling agent is 10-50 parts. , The organic solvent A is 15 to 45 parts.

On the basis of the above solution, further, the organic solvent A is any one or a combination of hydrocarbon solvents and alcohol solvents.

On the basis of the above solution, further, the hydrocarbon solvent is any one or a combination of two of toluene, xylene, and trimethylbenzene.

On the basis of the above solution, further, the alcohol solvent is any one or a combination of two of n-butanol, isobutanol, and phenethyl alcohol.

On the basis of the above solution, further, the nano particles are one of nano silica, nano titanium dioxide, nano zinc oxide or nano aluminum oxide.

On the basis of the above solution, further, the particle size of the nanoparticles is 10-40 nm.

On the basis of the above solution, further, the silane coupling agent is one of KBE-1003, KBM503, and KBM5103.

On the basis of the above solution, further, the solid content of the silyl (meth)acrylate copolymer is 55%.

On the basis of the above solution, further, the viscosity of the silyl (meth)acrylate copolymer is 10-15 poise.

On the basis of the above solution, further, the weight average molecular weight of the silyl (meth)acrylate copolymer is 10,000 to 15,000.

On the basis of the above solution, further, the nanoparticles modified by silane coupling agent, (meth)acrylate, and (meth)silyl acrylate include the following parts by weight of raw materials: The amount of nanoparticles modified by the coupling agent is 10-30 parts, the (meth)acrylate is 1-20 parts, the (meth)silyl acrylate is 20-40 parts, and the initiator is 1-20 parts. 5 parts, the organic solvent B is 10-50 parts.

On the basis of the above solution, further, the (meth)acrylate is any of methyl methacrylate methyl, ethyl acrylate, propyl methacrylate, butyl methacrylate, and isooctyl acrylate. One or more compositions.

On the basis of the above solution, further, the (meth)acrylate is 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate A combination of any one or more of the esters.

On the basis of the above solution, further, the structural formula of the silyl (meth)acrylate is as follows:

Wherein, R is H or CH ₃ , and R ₁ , R ₂ , and R ₃ are alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups having 1 to 20 carbon atoms.

On the basis of the above solution, further, the silyl (meth)acrylate is trimethylsilyl acrylate, triethylsilyl acrylate, triisopropylsilyl acrylate, tributyl silyl acrylate Ester, trimethylsilyl methacrylate, triethylsilyl methacrylate, triisopropylsilyl methacrylate, and tributylsilyl methacrylate Things.

On the basis of the above solution, further, the organic solvent B is any one or a combination of aromatic hydrocarbon solvents, ester solvents, ketone solvents or ether solvents.

On the basis of the above solution, further, the aromatic hydrocarbon solvent is any one or a combination of toluene and xylene.

On the basis of the above solution, further, the ester solvent is any one or a combination of two of butyl acetate and ethyl acetate.

On the basis of the above solution, further, the ketone solvent is any one or a combination of two of methyl ethyl ketone, methyl ethyl ketone, or cyclohexanone.

On the basis of the above solution, further, the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether.

On the basis of the above scheme, further, the initiator is benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile, azo Any one or a combination of diisovaleronitrile.

On the basis of the above solution, it further comprises the following parts by weight of raw materials: the silyl (meth)acrylate copolymer is 4-40 parts, the silane coupling agent, (meth)acrylate, The amount of silyl (meth)acrylate modified nanoparticles is 61-95 parts.

Compared with the prior art, an organic-inorganic nanocomposite anti-fouling coating for environment-friendly anti-fouling coatings and a preparation method thereof provided by the present invention have the following technical principles and beneficial effects:

1. The surface of the modified nanoparticles will be hydrolyzed to produce hydrophilicity, dissolve in seawater, and the dissolution rate is faster than the hydrolysis rate of the matrix resin SP-Si, which helps to renew the surface and is not conducive to the attachment of microorganisms.

2. The invention can effectively reduce the accumulation of marine organisms and reduce the adhesion of dirt.

3. It can self-renew the surface, does not contain antifouling agent and is environmentally friendly.

Description of the drawings

In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative labor.

Figure 1 is a schematic diagram of the structure of an organic-inorganic nanocomposite antifouling coating used in an environmentally friendly antifouling coating provided by the present invention;

Fig. 2 is a graph of the hydrolysis rate of an organic-inorganic nanocomposite antifouling coating for an environmentally friendly antifouling coating provided by the present invention.

Detailed ways

In order to make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments These are a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

The present invention also provides the following examples and comparative examples:

Table 1 Table of components in Examples 1-4

Table 2 Table of components in Examples 5-8

Among them, in Example 1, the following preparation materials were used:

The NPs use nano-silica with a particle size of 10 nm, the silane coupling agent (SCA) uses KBE503, the organic solvent A uses xylene, and the (meth) silyl acrylate uses trimethyl acrylate. Silyl ester, the (meth)acrylate uses methyl methacrylate, the initiator uses azobisisobutyronitrile, the organic solvent B uses butyl acetate; the (meth)acrylate silane The ester solution SPC adopts the (meth) silyl acrylate copolymer SP-Si solution prepared by the method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 12 poise, and a weight average molecular weight of 12,000; and the preparation method is as follows :

Step 1: Put organic solvent A and nanoparticles into a four-necked flask, disperse ultrasonically for 20 minutes, heat to 40℃ under nitrogen atmosphere, and then drop silane coupling agent (SCA) into the four-necked flask within 4 hours. ) And keep heating, after the addition is completed, repeat the centrifugal washing 3 times to obtain the nanoparticles (G-NPs) modified by the silane coupling agent (SCA);

Step 2: Add organic solvent B and silane coupling agent (SCA) modified nanoparticles (G-NPs) to the four-necked flask, heat it at 80°C under nitrogen atmosphere, and then within 6 hours, transfer to the four-necked flask. The mixture of (meth)acrylate, silyl (meth)acrylate, and initiator was dropped into the flask and kept heated. After the addition was completed, the centrifugal washing was repeated 3 times to obtain the silane coupling agent (SCA). ), (meth)acrylate and silyl (meth)acrylate modified nanoparticles (PG-NPs);

Step 3: Add the silyl (meth)acrylate copolymer solution to the dispersion tank, and add the silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate at a speed of 500rpm Modified nanoparticles (PG-NPs), followed by high-speed dispersion for 15 minutes, are ready.

In Example 2, the following preparation materials were used:

The NPs use nano-silica with a particle size of 15, the silane coupling agent (SCA) uses KBE503, the organic solvent A uses toluene, and the (meth) silyl acrylate uses triethyl acrylate. Silane ester, the (meth)acrylate uses ethyl acrylate, the initiator uses azobisisobutyronitrile, the organic solvent B uses butyl acetate; the (meth) silyl acrylate solution SPC The silyl (meth)acrylate copolymer SP-Si solution prepared by the method disclosed in the patent US7691938B2, with a solid content of 55%, a viscosity of 12 poise, and a weight average molecular weight of 12,000; and the following preparation method:

Step 1: Put the organic solvent A and nanoparticles into a four-necked flask, disperse it ultrasonically for 20 minutes, heat to 40°C under a nitrogen atmosphere, and then drop the silane coupling agent (SCA) into the four-necked flask within 3 hours. ) And keep heating, after the addition is completed, repeat the centrifugal washing 3 times to obtain the nanoparticles (G-NPs) modified by the silane coupling agent (SCA);

Step 2: Add organic solvent B and silane coupling agent (SCA) modified nanoparticles (G-NPs) into a four-necked flask, heat to 80℃ under nitrogen atmosphere, and then add to four-necked flask within 6 hours. The mixture of (meth)acrylate, silyl (meth)acrylate and initiator was dropped into the flask and kept heated. After the addition was completed, the centrifugal washing was repeated 3 times to obtain the silane coupling agent ( SCA), (meth)acrylate, and silyl (meth)acrylate modified nanoparticles (PG-NPs);

Step 3: Add the silyl (meth)acrylate copolymer solution to the dispersion tank, and add the silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate at a speed of 500rpm Modified nanoparticles (PG-NPs), followed by high-speed dispersion for 15 minutes, are ready.

In Example 3, the following preparation materials were used:

The NPs adopts nano-silica with a particle size of 20, the silane coupling agent (SCA) adopts KBM5103, the organic solvent A adopts xylene, and the (meth) silyl acrylate adopts trimethacrylate. Isopropylsilyl ester, the (meth)acrylate uses 2-hydroxybutyl acrylate, the initiator uses benzoyl peroxide, and the organic solvent B uses propylene glycol methyl ether; the (meth) The silyl acrylate solution SPC adopts the (meth) silyl acrylate copolymer SP-Si solution prepared by the method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 10 poise, and a weight average molecular weight of 10050; and The following preparation method:

Step 1: Put the organic solvent A and the nanoparticles into a four-necked flask, disperse ultrasonically for 20 minutes, heat to 40°C under a nitrogen atmosphere, and then drop the silane coupling agent (SCA) into the four-necked flask within 5 hours. ) And keep heating, after the addition is completed, repeat the centrifugal washing 3 times to obtain the nanoparticles (G-NPs) modified by the silane coupling agent (SCA);

Step 2: Add organic solvent B and silane coupling agent (SCA) modified nanoparticles (G-NPs) into the four-necked flask, heat to 85°C under nitrogen atmosphere, and then add to the four-necked flask within 6 hours. The mixture of (meth)acrylate, silyl (meth)acrylate and initiator was dropped into the flask and kept heated. After the addition was completed, the centrifugal washing was repeated 3 times to obtain the silane coupling agent ( SCA), (meth)acrylate, and silyl (meth)acrylate modified nanoparticles (PG-NPs);

Step 3: Add the silyl (meth)acrylate copolymer solution to the dispersion tank, and add the silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate at a speed of 500rpm Modified nanoparticles (PG-NPs), followed by high-speed dispersion for 15 minutes, are ready.

In Example 4, the following preparation materials were used:

The NPs use nano-silica with a particle size of 15, the silane coupling agent (SCA) uses KBE-1003, the organic solvent A uses toluene, and the (meth) silyl acrylate uses trimethyl acrylate. Methyl silyl ester, the (meth)acrylate uses 2-hydroxybutyl methacrylate, the initiator uses azobisisobutyronitrile, the organic solvent B uses butyl acetate; the (methyl) ) The silyl acrylate solution adopts the (meth) silyl acrylate copolymer SP-Si solution prepared by the method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 11 poise, and a weight average molecular weight of 11800; and The following preparation method:

Step 1: Put the organic solvent A and nanoparticles into a four-necked flask, disperse ultrasonically for 20 minutes, heat to 50°C under a nitrogen atmosphere, and then drop the silane coupling agent (SCA) into the four-necked flask within 4 hours. ) And keep heating, after the addition is completed, repeat the centrifugal washing 3 times to obtain the nanoparticles (G-NPs) modified by the silane coupling agent (SCA);

Step 2: Add organic solvent B and silane coupling agent (SCA) modified nanoparticles (G-NPs) into a four-necked flask, heat to 87°C under nitrogen atmosphere, and then add to four-necked flask within 8 hours. The mixture of (meth)acrylate, silyl (meth)acrylate and initiator was dropped into the flask and kept heated. After the addition was completed, the centrifugal washing was repeated 3 times to obtain the silane coupling agent ( SCA), (meth)acrylate, and silyl (meth)acrylate modified nanoparticles (PG-NPs);

Step 3: Add the silyl (meth)acrylate copolymer solution to the dispersion tank, and add the silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate at a speed of 500rpm Modified nanoparticles (PG-NPs), followed by high-speed dispersion for 15 minutes, are ready.

Among them, in Example 5, the following preparation materials were used:

The NPs use nano zinc oxide with a particle size of 20, the silane coupling agent (SCA) uses KBE-1003, the organic solvent A uses xylene, and the (meth) silyl acrylate uses triisoacrylate. Propyl silyl ester, the (meth)acrylate uses methyl methacrylate, the initiator uses azobisisobutyronitrile, the organic solvent B uses propylene glycol methyl ether; the (meth)acrylic acid The silyl ester solution SPC adopts the (meth) silyl acrylate copolymer SP-Si solution prepared by the method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 14 (10-15) poise, and a weight average molecular weight of 13040; and according to the following preparation method:

Step 1: Put organic solvent A and nanoparticles into a four-necked flask, disperse ultrasonically for 20 minutes, heat to 48℃ under nitrogen atmosphere, and then drop silane coupling agent (SCA) into the four-necked flask within 5 hours. ) And keep heating, after the addition is completed, repeat the centrifugal washing 3 times to obtain the nanoparticles (G-NPs) modified by the silane coupling agent (SCA);

Step 2: Add organic solvent B and silane coupling agent (SCA) modified nanoparticles (G-NPs) into the four-necked flask, heat to 90°C under nitrogen atmosphere, and then add to the four-necked flask within 7 hours. The mixture of (meth)acrylate, silyl (meth)acrylate and initiator was dropped into the flask and kept heated. After the addition was completed, the centrifugal washing was repeated 3 times to obtain the silane coupling agent ( SCA), (meth)acrylate, and silyl (meth)acrylate modified nanoparticles (PG-NPs);

Step 3: Add the silyl (meth)acrylate copolymer solution to the dispersion tank, and add the silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate at a speed of 500rpm Modified nanoparticles (PG-NPs), followed by high-speed dispersion for 15 minutes, are ready.

Among them, in Example 6, the following preparation materials were used:

The NPs adopts nanometer titanium dioxide with a particle size of 30, the silane coupling agent (SCA) adopts KBE-1003, the organic solvent A adopts xylene, and the (meth) silyl acrylate adopts trimethacrylate. Isopropyl silyl ester, the (meth)acrylate uses ethyl acrylate, the initiator uses tert-butyl benzoyl peroxide, and the organic solvent B uses propylene glycol methyl ether; the (methyl) The silyl acrylate solution SPC adopts the (meth) silyl acrylate copolymer SP-Si solution prepared by the method published in the patent US7691938B2, and has a solid content of 55%, a viscosity of 13 poise, and a weight average molecular weight of 12,800; and The following preparation method:

Step 1: Put the organic solvent A and the nanoparticles into a four-necked flask, disperse ultrasonically for 20 minutes, heat to 47°C under a nitrogen atmosphere, and then drop the silane coupling agent (SCA) into the four-necked flask within 4 hours. ) And keep heating, after the addition is completed, repeat the centrifugal washing 3 times to obtain the nanoparticles (G-NPs) modified by the silane coupling agent (SCA);

Step 2: Add organic solvent B and silane coupling agent (SCA) modified nanoparticles (G-NPs) into the four-necked flask, heat to 90°C under nitrogen atmosphere, and then add to the four-necked flask within 6 hours. The mixture of (meth)acrylate, silyl (meth)acrylate and initiator was dropped into the flask and kept heated. After the addition was completed, the centrifugal washing was repeated 3 times to obtain the silane coupling agent ( SCA), (meth)acrylate, and silyl (meth)acrylate modified nanoparticles (PG-NPs);

Step 3: Add the silyl (meth)acrylate copolymer solution to the dispersion tank, and add the silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate at a speed of 500rpm Modified nanoparticles (PG-NPs), followed by high-speed dispersion for 15 minutes, are ready.

Among them, in Example 7, the following preparation materials were used:

The NPs use nanometer titanium dioxide with a particle size of 20, the silane coupling agent (SCA) uses KBM503, the organic solvent A uses xylene, and the (meth) silyl acrylate uses trimethyl methacrylate. Silyl ester, the (meth)acrylate uses 2-hydroxypropyl acrylate, the initiator uses azobisisobutyronitrile, the organic solvent B uses propylene glycol methyl ether; the (meth)acrylate methyl Silane ester solution SPC adopts (meth) silyl acrylate copolymer SP-Si solution prepared by the method published in patent US7691938B2, and has a solid content of 55%, a viscosity of 13 poise, and a weight average molecular weight of 13,500; and the preparation is as follows method:

Step 1: Put the organic solvent A and nanoparticles into a four-necked flask, disperse ultrasonically for 20 minutes, heat to 55°C under a nitrogen atmosphere, and then drop the silane coupling agent (SCA) into the four-necked flask within 4 hours. ) And keep heating, after the addition is completed, repeat the centrifugal washing 3 times to obtain the nanoparticles (G-NPs) modified by the silane coupling agent (SCA);

Step 2: Add organic solvent B and silane coupling agent (SCA) modified nanoparticles (G-NPs) into a four-necked flask, heat to 110°C under nitrogen atmosphere, and then add to the four-necked flask within 9 hours. The mixture of (meth)acrylate, silyl (meth)acrylate and initiator was dropped into the flask and kept heated. After the addition was completed, the centrifugal washing was repeated 3 times to obtain the silane coupling agent ( SCA), (meth)acrylate, and silyl (meth)acrylate modified nanoparticles (PG-NPs);

Step 3: Add the silyl (meth)acrylate copolymer solution to the dispersion tank, and add the silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate at a speed of 500rpm Modified nanoparticles (PG-NPs), followed by high-speed dispersion for 15 minutes, are ready.

Among them, in Example 8, the following preparation materials were used:

The NPs use nanometer aluminum oxide with a particle size of 30, the silane coupling agent (SCA) uses KBM5103, the organic solvent A uses xylene, and the (meth) silyl acrylate uses methacrylic acid. Triisopropylsilyl ester, the (meth)acrylate is 2-hydroxypropyl acrylate, the initiator is azobisisoheptonitrile, and the organic solvent B is propylene glycol methyl ether; The silyl acrylate solution SPC adopts the (meth) silyl acrylate copolymer SP-Si solution prepared by the method disclosed in patent US7691938B2, and has a solid content of 55%, a viscosity of 15 poise, and a weight average molecular weight of 14,500; And follow the preparation method below:

Step 1: Put organic solvent A and nanoparticles into a four-necked flask, disperse ultrasonically for 20 minutes, heat to 60℃ under nitrogen atmosphere, and then drop silane coupling agent (SCA) into the four-necked flask within 6 hours. ) And keep heating, after the addition is completed, repeat the centrifugal washing 3 times to obtain the nanoparticles (G-NPs) modified by the silane coupling agent (SCA);

Step 2: Add organic solvent B and silane coupling agent (SCA) modified nanoparticles (G-NPs) into a four-necked flask, heat to 100°C under nitrogen atmosphere, and then add to four-necked flask within 8 hours. The mixture of (meth)acrylate, silyl (meth)acrylate and initiator was dropped into the flask and kept heated. After the addition was completed, the centrifugal washing was repeated 3 times to obtain the silane coupling agent ( SCA), (meth)acrylate, and silyl (meth)acrylate modified nanoparticles (PG-NPs);

Step 3: Add the silyl (meth)acrylate copolymer solution to the dispersion tank, and add the silane coupling agent (SCA), (meth)acrylate, and silyl (meth)acrylate at a speed of 500rpm Modified nanoparticles (PG-NPs), followed by high-speed dispersion for 15 minutes, are ready.

In Comparative Example 1, 75 parts by weight of silyl (meth)acrylate and 25 parts by weight of unmodified nanoparticles (NPs) were used;

Wherein, the NPs adopts nano-silica with a particle size of 20, and the silyl (meth)acrylate solution adopts the silyl (meth)acrylate copolymer SP-Si solution prepared by the method disclosed in patent US7691938B2 , And the solid content is 55%, the viscosity is 12 poise, the weight average molecular weight is 12800; and it is obtained by the following preparation method:

Add the silyl (meth)acrylate copolymer solution to the dispersion tank, add unmodified nanoparticles (NPs) at a rotation speed of 500 rpm, and then disperse at a high speed for 15 minutes to obtain.

In Comparative Example 2, 75 parts by weight of silyl (meth)acrylate and 25 parts by weight of silane coupling agent (SCA) modified nanoparticles (G-NPs) were used;

Wherein, the NPs uses nano-silica with a particle size of 10, the silane coupling agent (SCA) uses KBE503, the organic solvent A uses xylene, and the (meth) silyl acrylate solution uses The silyl (meth)acrylate copolymer SP-Si solution prepared by the method disclosed in the patent US7691938B2 has a solid content of 55%, a viscosity of 12 poise, and a weight average molecular weight of 12,000; and is obtained by the following preparation method:

Step 1: Put organic solvent A and nanoparticles into a four-necked flask, disperse ultrasonically for 20 minutes, heat to 40℃ under nitrogen atmosphere, and then drop silane coupling agent (SCA) into the four-necked flask within 4 hours. ) And keep heating, after the addition is completed, repeat the centrifugal washing 3 times to obtain the nanoparticles (G-NPs) modified by the silane coupling agent (SCA);

Step 2: Add the silyl (meth)acrylate copolymer solution to the dispersion tank, add the silane coupling agent (SCA) modified nanoparticles (G-NPs) at 500 rpm, and then disperse at high speed for 15 minutes. Immediately.

Coat the sample to be tested and the comparative sample on a 2.5cm×6cm glass slide with a coating area of 2.5cm×6cm. Place the sample to be tested in a dry environment at 30℃. Completely dry, keep the dry film thickness at about 100μm, and place it in flowing artificial seawater (25℃) for testing. The weight loss rate per unit time of the copolymer is used to express the hydrolysis rate, where:

Weight loss rate=(100×(W ₀ -W _dry ))/(D*W ₀ );

W ₀ is the total weight of the dry film before the test; W _dry is the total weight of the dry film after a certain test time; D is the number of days soaked in water.

Figure 1 is a schematic diagram of the structure of the organic-inorganic nanocomposite antifouling coating; the modified nanoparticles can be continuously hydrolyzed from the polished matrix resin and faster than the matrix resin, making the surface unfavorable for the adhesion of marine organisms and conducive to fouling Desorption,

Figure 2 is a graph of the hydrolysis rate of the organic-inorganic nanocomposite antifouling coating, which shows that the coating in the embodiment can stably renew the surface layer.

Table 3 Coating contact angle test results

According to Table 3, it can be seen that the organic-inorganic nanocomposite antifouling coating for the environmentally friendly antifouling coating provided by the present invention has more significant and strong hydrophobicity than the comparative sample (except for Comparative Example 2).

It can be seen from Figure 2 that the hydrolysis rate of the copolymer SP-Si without nanoparticles is very low, and the surface renewal rate is very slow, while the hydrolysis rate of the unmodified nanoparticles in the comparative example is too fast, after about 20 days Cracking, the remaining examples have a good moderate stable hydrolysis rate.

The test results of the organic-inorganic nanocomposite antifouling coating are shown in Table 4.

Table 4 Antifouling results of organic-inorganic nanocomposite antifouling coating (6 months for hanging the board)

Test items Example 1 Example 2 Example 3 Example 4 Comparative example 1 SP-Si score 88 90 93 95 70 50

Test items Example 5 Example 6 Example 7 Example 8 Comparative example 2 \ score 89 87 94 85 73 \

The test is carried out in accordance with the national standard GB/T 5370-2007 "Test Method for Shallow Sea Immersion of Antifouling Paint Samples".

It can be seen from Table 4 that the organic-inorganic nanocomposite anti-fouling coating used for the environmentally friendly anti-fouling coating provided by the present invention has a better anti-fouling effect than the comparative sample.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or equivalently replace some or all of the technical features; these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. range.

Claims (50)

An organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings, which is characterized in that it comprises the following preparation raw materials: modified by silane coupling agent, (meth)acrylate, and (meth)silyl acrylate Sexual nanoparticles and silyl (meth)acrylate copolymer. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 1, characterized in that it comprises the following parts by weight of raw materials: the silyl (meth)acrylate copolymer is 4~ 40 parts, the number of the nanoparticles modified by silane coupling agent, (meth)acrylate, and silyl (meth)acrylate is 61-95 parts. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 1 or 2, characterized in that the silane coupling agent, (meth)acrylate, (meth)acrylic acid The silyl ester-modified nanoparticles include the following preparation materials: nanoparticles modified with a silane coupling agent, (meth)acrylate, silyl (meth)acrylate, initiator and organic solvent B. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 3, wherein the silane coupling agent, (meth)acrylate, (meth)acrylate silane The ester-modified nanoparticles include the following parts by weight of raw materials: the nanoparticles modified by the silane coupling agent are 10-30 parts, the (meth)acrylate is 1-20 parts, the (methyl) ) 20-40 parts of silyl acrylate, 1-5 parts of the initiator, and 10-50 parts of the organic solvent B. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 3 or 4, wherein the (meth)acrylate is methyl methacrylate methyl or ethyl acrylate , Propyl methacrylate, butyl methacrylate, and isooctyl acrylate. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 3-5, wherein the (meth)acrylate is (meth)acrylic acid 2-hydroxyl A combination of any one or more of ethyl ester, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 3-6, wherein the structural formula of the silyl (meth)acrylate is as follows:

Wherein, R is H or CH ₃ , and R ₁ , R ₂ , and R ₃ are alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups having 1 to 20 carbon atoms. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 3-7, wherein the silyl (meth)acrylate is trimethylsilyl acrylate Ester, triethylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, trimethylsilyl methacrylate, triethylsilyl methacrylate, triisopropyl methacrylate A combination of any one or more of propyl silyl ester and tributyl silyl methacrylate. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 3-8, wherein the organic solvent B is aromatic hydrocarbon solvents, ester solvents, ketones Either one or a combination of solvents or ether solvents. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 9, wherein the aromatic hydrocarbon solvent is any one or a combination of toluene and xylene . The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 9, wherein the ester solvent is any one or two of butyl acetate and ethyl acetate combination. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 9, wherein the ketone solvent is any one of methyl ethyl ketone, methyl ethyl ketone, or cyclohexanone A combination of one or two. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 9, wherein the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 3-13, wherein the initiator is benzoyl peroxide and tertiary benzoyl peroxide. Any one or a combination of butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile, and azobisisovaleronitrile. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 3-14, wherein the nanoparticles modified by a silane coupling agent comprise the following preparation raw materials: Nano particles, silane coupling agent, organic solvent A. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 15, wherein the nanoparticles modified by the silane coupling agent comprise the following raw materials by weight: The particles are 5-25 parts, the silane coupling agent is 10-51 parts, and the organic solvent A is 15-45 parts. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 15 or 16, wherein the organic solvent A is any one or both of hydrocarbon solvents and alcohol solvents. Kind of composition. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 17, wherein the hydrocarbon solvent is any one or two of toluene, xylene, and trimethylbenzene combination. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 17, wherein the alcohol solvent is any one of n-butanol, isobutanol, phenethyl alcohol or A combination of two. The organic-inorganic nano-composite anti-fouling coating for environmentally friendly anti-fouling coatings according to any one of claims 15-19, wherein the nanoparticles are nano-silica, nano-titanium dioxide, nano-zinc oxide or One of nanometer aluminum oxide. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 15-20, wherein the particle size of the nanoparticles is 10-40 nm. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 15-21, wherein the silane coupling agent is one of KBE-1003, KBM503, KBM5103 Kind. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 1-22, wherein the solid content of the silyl (meth)acrylate copolymer is 55 %. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 1-23, wherein the viscosity of the silyl (meth)acrylate copolymer is 10~ 15 berths. The organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 1-24, wherein the weight average molecular weight of the silyl (meth)acrylate copolymer is 10000～15000. A preparation method of organic-inorganic nano composite anti-fouling coating for environment-friendly anti-fouling coating, which is characterized in that it comprises the following steps: Add the silyl (meth)acrylate copolymer solution to the preparation container, add nanoparticles modified with silane coupling agent, (meth)acrylate, and silyl (meth)acrylate while dispersing, and disperse, Immediately. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 26, characterized in that the silane coupling agent, (meth)acrylate, (meth) The silyl acrylate modified nanoparticles include the following preparation steps: Add organic solvent B and nanoparticles modified by silane coupling agent to the preparation container, heat to 80-115°C under a protective gas atmosphere, and then drip into the preparation container within 5-10 hours. (Methyl) acrylate, (meth) silyl acrylate, and the mixture of initiator and keep heated. After the addition is complete, centrifuge and wash to obtain the silane coupling agent, (meth) acrylate, (meth) acrylate, (meth) acrylate, (meth) acrylate, and (meth) acrylate. Silyl acrylate modified nanoparticles. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 27, wherein the nanoparticle modified by a silane coupling agent comprises the following preparation steps: Put the organic solvent A and the nanoparticles into the preparation container, ultrasonically disperse, heat to 40～60℃ in a protective gas atmosphere, and then drop the silane coupling agent into the preparation container within 3-6 hours and keep it After heating and dropping, centrifugal washing is performed to obtain nanoparticles modified by the silane coupling agent. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 27 or 28, wherein the nanoparticles modified by the silane coupling agent comprise the following parts by weight Raw materials: the nano particles are 5-25 parts, the silane coupling agent is 10-51 parts, and the organic solvent A is 15-45 parts. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 28 or 29, wherein the organic solvent A is any one of hydrocarbon solvents and alcohol solvents A combination of one or two. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 30, wherein the hydrocarbon solvent is any one of toluene, xylene, trimethylbenzene or A combination of two. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 30, wherein the alcohol solvent is any of n-butanol, isobutanol, and phenethyl alcohol. One or two combinations. The method for preparing an organic-inorganic nano composite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 28-32, characterized in that: the nano particles are nano silica, nano titanium dioxide, nano One of zinc oxide or nano aluminum oxide. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 28-33, wherein the particle size of the nanoparticles is 10-40 nm. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 28-34, wherein the silane coupling agent is KBE-1003, KBM503, KBM5103 One of them. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 28-35, wherein the solidification of the silyl (meth)acrylate copolymer The content is 55%. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 28-36, wherein the viscosity of the silyl (meth)acrylate copolymer is It is 10-15 poise. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 28-37, wherein the weight of the silyl (meth)acrylate copolymer is The average molecular weight is 10,000 to 15,000. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 26 or 27, wherein the silane coupling agent, (meth)acrylate, (formaldehyde) The silyl acrylate-modified nanoparticles include the following raw materials in parts by weight: the silane coupling agent-modified nanoparticles are 10-30 parts, the (meth)acrylate is 1-20 parts, The silyl (meth)acrylate is 20-40 parts, the initiator is 1-5 parts, and the organic solvent B is 10-50 parts. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 27, wherein the (meth)acrylate is methyl methacrylate, methyl methacrylate, and ethyl acrylate. A combination of any one or more of esters, propyl methacrylate, butyl methacrylate, and isooctyl acrylate. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 27-40, wherein the (meth)acrylate is (meth)acrylic acid A combination of any one or more of 2-hydroxyethyl, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 27-41, wherein the structural formula of the silyl (meth)acrylate is as follows:

Wherein, R is H or CH ₃ , and R ₁ , R ₂ , and R ₃ are alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups having 1 to 20 carbon atoms. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 27-42, wherein the silyl (meth)acrylate is trimethyl acrylate Silyl acrylate, triethyl silyl acrylate, triisopropyl silyl acrylate, tributyl silyl acrylate, trimethyl silyl methacrylate, triethyl silyl methacrylate, methyl A combination of any one or more of triisopropylsilyl acrylate and tributylsilyl methacrylate. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 27-43, wherein the organic solvent B is an aromatic hydrocarbon solvent or an ester solvent , Any one or a combination of ketone solvents or ether solvents. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 44, wherein the aromatic hydrocarbon solvent is any one or two of toluene and xylene Compositions. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 44, wherein the ester solvent is any one of butyl acetate, ethyl acetate, or A combination of two. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 44, wherein the ketone solvent is methyl ethyl ketone, methyl ethyl ketone or cyclohexanone. Any one or a combination of both. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 44, wherein the ether solvent is propylene glycol methyl ether or propylene glycol ethyl ether. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to any one of claims 27-40, wherein the initiator is benzoyl peroxide or benzene peroxide. Any one or a combination of formyl tert-butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile, and azobisisovaleronitrile. The method for preparing an organic-inorganic nanocomposite antifouling coating for environmentally friendly antifouling coatings according to claim 26, characterized in that it comprises the following parts by weight of raw materials: the silyl (meth)acrylate copolymer The amount is 4-40 parts, and the amount of the nanoparticles modified by silane coupling agent, (meth)acrylate, and silyl (meth)acrylate is 61-95 parts.

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